Herbicide compositions

ABSTRACT

Certain urea-sulfuric acid components, comprised of urea and sulfuric acid in a 1/4 to 7/4 molar ratio, contain a monourea adduct of sulfuric acid, which is catalytically active for promoting organic chemical reactions. The invention provides methods employing such urea-sulfuric acid components for catalyzing organic reactions such as oxidation, oxidative addition, reduction, reductive addition, esterification, transesterification, hydrogenation, isomerization (including racemization of optical isomers), alkylation, polymerization, demetallization of organometallics, nitration, Friedel-Crafts reactions, hydrolysis. Novel catalysts are disclosed which involve combinations of the urea-sulfuric component with one or more transition metal halides and/or with one or more surfactants. The surfactant-containing compositions are particularly useful for the treatment of materials containing lipophilic substances. Novel compositions containing the urea-sulfuric acid component and one or more organic reactants are also disclosed.

This application is a continuation, of U.S. application Ser. No.06/783,368, filed Oct. 3, 1985 now U.S. Pat. No. 4,910,179.

RELATED APPLICATIONS

This application is a divisional application of my copending U.S.application Ser. No. 453,496 filed Dec. 27, 1982 for Acid CatalyzedReactions and Compositions for Use Therein which was acontinuation-in-part of my copending applications Ser. No. 442,296,SYSTEMIC HERBIDICAL COMPOSITION AND METHODS OF USE, filed Nov. 17, 1982;Ser. No. 444,667, METHODS FOR CONTROLLING VEGETATION, filed Nov. 26,1982; Ser. No. 331,001, NONCORROSIVE UREASULFURIC ACID COMPOSITIONS,filed Dec. 15, 1981, now U.S. Pat. No. 4,402,852; Ser. No. 330,904,NONCORROSIVE UREA-SULFURIC ACID REACTION PRODUCTS, filed Dec. 15, 1981,now U.S. Pat. No. 4,404,116; Ser. No. 318,629, METHOD OF PRODUCINGCONCENTRATED UREA-SULFURIC ACID REACTION PRODUCTS, filed Nov. 5, 1981,now U.S. Pat. No. 4,445,925; Ser. No. 318,368, TOPICAL FERTILIZATIONMETHODS AND COMPOSITIONS FOR USE THEREIN, filed Nov. 5, 1981, now U.S.Pat. No. 4,447,253; and Ser. No. 318,343, METHOD OF PRODUCINGUREA-SULFURIC ACID REACTION PRODUCTS, filed Nov. 5, 1981, now U.S. Pat.No. 4,397,675.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the field of acid-catalyzed organic reactionsand particularly to methods of conducting acid-catalyzed reactions oforganic compounds which reactions are promoted by strong acids. Theinvention also relates to novel acidic compositions useful in suchreactions.

2. Description of the Art

Both urea and sulfuric acid are well known and are widely used innumerous industries for a variety of purposes, including their use infertilizers, soil adjuvants, chemical treating agents, chemicalprecursors, and reactants. The ability of sulfuric acid to catalyze avariety of organic reactions is also known. Urea and sulfuric acid aresometimes useful in combination, particularly in the agriculturalindustry when simultaneous addition of urea and sulfur to the soil isdesired.

It is also known that urea and sulfuric acid will combine to formadducts including the monourea-sulfuric acid adduct and thediurea-sulfuric acid adduct. For instance, D. F. du Toit, Verslag Akad.Wetenschappen, 22, 573-4 (abstracted in Chemical Abstracts, 8, 2346,1914) disclosed that urea forms certain compounds with oxalic, acetichydrochloric, nitric and sulfuric acids. L. H. Dalman, "Ternary Systemsof Urea and Acid. I. Urea, Nitric Acid and Water. II. Urea, SulfuricAcid and Water. III. Urea, Oxalic Acid and Water"; JACS, 56, 549-53(1934), disclosed the phase relationships between the solid phase andsaturated solutions containing urea and sulfuric acid at 10° C. and 25°C. The Sulfur Institute, Sulfur Institute Bulletin No. 10 (1964),"Adding Plant Nutrient Sulfur to Fertilizer", disclosed that urea reactswith sulfuric acid to form two complexes of "urea sulfate" which areuseful fertilizers. Methods of manufacturing certain combinations ofurea and sulfuric acid are disclosed by Verdegaal et al. in U.S. Pat.No. 4,310,343 and by Jones in U.S. Pat. No. 4,116,664.

A wide variety of organic conversions are catalyzed by theproton-donating ability of strong acids. Such reactions have beenextensively investigated and have been widely discussed in theliterature. For instance, the Kirk-Othmer Encyclopedia of ChemicalTechnology, Third Edition, John Wiley and Sons, New York, 1980,discusses a variety of organic reactions that are catalyzed by strongacids including mineral acids, transition metal halides such asFriedel-Crafts catalysts, conjugate Friedel-Crafts catalysts, andothers. Kirk-Othmer defines acid-catalyzed reactions as those in which aproton is transferred from the catalyst to the reactant which is therebyconverted to an unstable state which immediately leads to the reactionunder consideration. (Volume 5, page 33). While the proton donationmechanism of acid-catalyzed reactions referred to in Kirk-Othmer may ormay not account for the reactions that take place in all acid-catalyzedreactions, it is known that strong acids promote numerous reactionsincluding oxidative addition, reductive addition, esterification,transesterification, hydrogenation, isomerization (includingracemization of optical isomers), hydrolysis and alcoholisis,alkylation, olefin polymerization, Friedel-Crafts reactions,demetalization of organics, and nitration reactions, among others.Strong acids known to be capable of promoting such acid-catalyzedorganic reactions include sulfuric acid, nitric acid, hydrochloric acid,transition metal halides including the so-called Friedel-Craftscatalysts, for example, the halides of aluminum, gallium, boron,titanium, vanadium, tin and others, and conjugate Friedel-Craftscatalysts also known as Bronsted-Lewis superacid mixtures (Kirk-Othmer,V. 11, 295) such as mineral acid adducts of transition metal halides.

All of the known strong acid catalysts and the methods involving theiruse for the promotion of acid-catalyzed organic reactions suffer fromone or more disadvantages. For instance, the strong mineral acidspromote side reactions which form undesired by-products, destroy theorganic feed material or product, and/or consume or deactivate thecatalyst. Sulfuric acid is a strong sulfating, sulfonating, oxidizing,and dehydrating agent, and by virtue of those activities, it is consumedin most organic reactions by side reactions involving these mechanisms.Furthermore, the sulfonating and oxidizing activities of sulfuric acidresults in the sulfonation and oxidation of organic feedstocks and/orproducts. Similar deficiencies exist with the other strong mineral acidssuch as hydrochloric and nitric acids. Hydrochloric acid chlorinates thereactants and thereby consumes the feed to produce unwanted chlorinatedby-products. Nitric acid oxidizes and/or nitrates organic compounds.Hydrofluoric acid fluorinates organic reactants and products. Thetransition metal halides, including the Friedel-Crafts catalysts, aredifficult to handle in that they must be isolated from water andreducing agents. Such catalysts also halogenate organic feedstocks andproducts.

Accordingly, a need exists for improved methods of conductingacid-catalyzed organic reactions and for improved acid catalysts for usein such reactions which will promote the desired acid-catalyzed organicreaction yet reduce or eliminate the side reactions normally associatedwith acid-catalyzed organic reactions.

It is therefore a principal object of this invention to provide novelmethods for the acid-catalyzed conversion of organic compounds.

Another object is the provision of novel methods for conductingacid-catalyzed reactions of organic compounds in the presence ofsulfuric acid.

Another object of this invention is the provision of novel acidcatalysts comprising sulfuric acid which are effective for conductingacid-catalyzed organic reactions.

Another object of this invention is the provision of novel compositionswhich are useful for conducting acid-catalyzed organic reactions.

Another object of this invention is the provision of novel catalystscomprising sulfuric acid which have improved activity in the presence oflipophilic materials.

Yet another objective of this invention is the provision of novelmethods for catalyzing organic reactions with sulfuric acid.

Another object is the provision of novel methods for the oxidativeaddition of organic compounds.

Yet another object is the provision of novel methods for the reductiveaddition of organic compounds.

Another object is the provision of novel sulfuric acid-containingcompositions useful for conducting organic reactions.

Another object is the provision of novel methods for the esterificationand transesterification of organic compounds.

Yet another object of this invention is the provision of novel methodsfor hydrogenating organic compounds containing olefinic unsaturation.

Another object is the provision of novel methods for isomerizing organiccompounds.

Yet another object is the provision of novel methods for the hydrolysis,alcoholisis, thiolosis, and amination of organic compounds.

Another object is the provision of novel methods for the alkylation oforganic compounds.

Yet another object is the provision of novel methods for polymerizingolefinic compounds.

Yet another object is the provision of novel conjugate Friedel-Craftscatalysts.

Another object is the provision of novel Friedel-Crafts catalyzedorganic reactions.

Yet another object of this invention is the provision of novel methodsfor demetalizing organic compounds.

Another object is the provision of novel methods for nitrating organiccompounds.

Other objects, aspects and advantages of this invention will be apparentto one skilled in the art in view of the following disclosure and theappended claims.

SUMMARY OF THE INVENTION

Briefly, the invention provides novel (1) surfactant-containing catalystcompositions suitable for promoting acid-catalyzed organic reactions,(2) conjugate Friedel-Crafts acid catalysts suitable for promotingacid-catalyzed organic reactions, (3) reactant-containing compositionscontaining urea, sulfuric acid, and one or more reactants useful forconducting organic reactions, and (4) methods of conductingacid-catalyzed organic reactions.

It has been discovered in the present invention that certain ureasulfuric acid components, comprising urea and sulfuric acid combined ina molar ratio of about 1/4 to about 7/4, are highly useful as catalysts,particularly for the promotion of organic reactions. Within this rangeof molar ratios, at least about 25 percent of the sulfuric acid presentin the urea-sulfuric acid component will be in the form of the monoureaadduct of sulfuric acid, which adduct is the active acid catalyst usefulherein.

Among the novel catalysts of the present invention are compositionscontaining the urea-sulfuric acid component in combination with asurfactant. Such catalysts are especially useful for promoting chemicalreactions involving relatively lipophilic organic materials, sincesurfactants accentuate the activity of the urea-sulfuric acid componenttoward such materials.

Also provided in the invention are conjugate Friedel-Crafts catalystscontaining combinations of the urea-sulfuric acid component describedabove, with or without surfactant, and one or more transition metalhalides.

Novel reactant-containing compositions are also provided containing thedescribed urea-sulfuric acid component, with or without a surfactant,and one or more reactants which reactants are useful in conductingorganic reactions.

The novel methods of this invention involve the acid-catalyzed reactionsof one or more organic compounds by contacting the organic compound orcompounds with a urea-sulfuric acid component which comprises a mixtureof urea and sulfuric acid in which the molar ratio of urea to sulfuricacid is within the range of about 1/4 to about 7/4 and in which at leastabout 25 percent of the sulfuric acid is present as themonourea-sulfuric acid adduct. The acid-catalyzed conversions can beconducted in the presence of novel surfactant-containing urea-sulfuricacid component described above. The use of the novelsurfactant-containing catalyst of this invention is advantageous in thecatalysts of many acid-catalyzed organic reactions, particularly thosein which the more lipophilic, i.e., hydrophobic materials are present.The surfactant contained in the novel catalysts accentuates the activityof the urea-sulfuric acid component toward more lipophilic substrates.Similarly, the novel conjugate acid catalysts of this invention can beemployed to catalyze the acid-catalyzed reactions involved in the novelmethods of this invention.

In particular, the novel methods of this invention involve theconversion of organic materials, at least in part, by the acid-catalyticactivity of sulfuric acid. Thus, they include all acid-catalyzed organicreactions that are catalyzed by sulfuric acid, such as

(a) oxidation of one or more organic compounds in the presence of anoxidant;

(b) reduction of one or more organic compounds by reaction with areducing agent such as hydrogen;

(c) hydrolysis of one or more organic compounds by reaction with waterand/or one or more alcohols and/or thiols;

(d) oxidative addition of one or more organic compounds by reaction withan oxidant;

(e) reductive addition of organic compounds by reaction with a reducingagent;

(f) esterification of amides, nitriles, carboxylic acids, acyl halides,thiocarboxylic acids, and/or carboxylic acid anhydrides by reaction withalcohols and/or thiols;

(g) hydrogenation of organic compounds containing carbon-to-carbonunsaturation by reaction with hydrogen;

(h) alkylation of organic compounds by reaction with an organicalkylating agent having at least one carbon-to-carbon olefinic bond;

(i) polymerization of organic compounds containing olefinic unsaturationin the presence of an oxidant;

(j) Friedel-Crafts reactions of organic compounds with hydrocarbylhalides;

(k) isomerization of hydrocarbons having four to about twenty carbonatoms per molecule;

(l) demetallization of organo-metal compounds by reaction with waterand/or alcohols; and

(m) nitration of organic compounds by reaction with a nitrating agentsuch as nitric oxide.

The methods and compositions of this invention eliminate most, if notall, of the deficiencies associated with the acid-catalyzed conversionof organic compounds in the presence of sulfuric acid. The use of theurea-sulfuric acid components in the methods of this invention minimizesor completely eliminates the undesirable oxidizing and sulfonatingactivity of sulfuric acid yet retains the strong proton donating abilityof sulfuric acid. Thus, the sulfuric acid contained in the urea-sulfuricacid component is not destroyed during acid-catalyzed organic reactionsdue to sulfonation, oxidation or other reactions associated withsulfuric acid. At the same time, organic feed materials are notdestroyed or converted to undesirable by-products by the side reactionsusually associated with sulfuric acid. All of these benefits exist withall forms of the urea-sulfuric acid component employed in the methods ofthis invention, including the novel surfactant-containing urea-sulfuricacid catalysts of this invention and the novel conjugate transitionmetal halide catalysts of this invention. Moreover, the novelsurfactant-containing urea-sulfuric acid components of this inventionexhibit improved catalytic activity for the conversion of organiccompounds in accordance with the methods of this invention, particularlyfor the conversion of more lipophilic compounds and the conversion oforganic materials which contain lipophilic matter, such as fats, waxes,and higher molecular weight organic substances.

DETAILED DESCRIPTION OF THE INVENTION

This invention provides novel (1) surfactant-containing urea-sulfuricacid combinations which are effective acid catalysts for promotingorganic conversions, (2) conjugate Friedel-Crafts catalysts whichcomprise combinations of transition metal halides and the describedurea-sulfuric acid components, (3) compositions containing the describednovel catalysts of this invention, with or without surfactant, and oneor more reactants which reactants are useful in conducting organicreactions, and (4) methods of conducting acid-catalyzed organicreactions, particularly organic reactions that are known to be catalyzedby sulfuric acid. The urea-sulfuric acid components employed in themethods of this invention contain a combination of urea and sulfuricacid in which the molar ratio of urea to sulfuric acid is within therange of about 1/4 to about 7/4. Within this range of molar ratios, atleast about 25 percent of the sulfuric acid is present as themonourea-sulfuric acid adduct. In one embodiment, the urea-sulfuric acidcomponent may optionally contain a surfactant. Surfactants increase theactivity of the urea-sulfuric acid component toward organic materialsand particularly toward organic materials that contain lipophilicconstituents such as fats, oils, waxes and the like. The urea-sulfuricacid component, with or without surfactant, may also be combined withone or more organic or inorganic reactants, which reactants participatein the desired organic reaction, to form a composition useful inconducting the desired organic reaction. In another embodiment, theurea-sulfuric acid component, with or without surfactants, can becombined with a conventional transition metal halide catalyst to form aconjugate Friedel-Crafts catalyst useful in the methods of thisinvention.

The methods of this invention can be employed to effect theacid-catalyzed conversion of organic compounds. In particular, themethods of this invention can be employed to catalyze the acid-catalyzedconversion of any organic material that can be converted by sulfuricacid catalysts, and usually without the occurrence of undesirable sidereactions normally associated with the use of sulfuric acid.Illustrative of acid-catalyzed reactions that can be effected by themethods of this invention are oxidation, particularly oxidative additionreactions; esterification; transesterification; hydrogenation;isomerization, including racemization of optical isomers; hydrolysis andalcoholisis by reaction with water, alcohols, or thiols; alkylation;olefin polymerization; Friedel-Crafts reactions; demetalization; andnitration. In accordance with the methods of this invention,acid-catalyzed conversions are conducted by contacting the organicreactant or reactants to be converted with the urea-sulfuric acidcomponent in the form of a solution in water or other solvents or as amolten mixture of urea and sulfuric acid.

The urea-sulfuric acid components employed in the methods of thisinvention are reaction products of urea and sulfuric acid in which themolar ratio of urea to sulfuric acid is within the range of about 1/4 toabout 7/4. In such components, at least about 25 percent of the sulfuricacid is present as the monourea-sulfuric acid adduct. These componentsmay be employed in the methods disclosed herein, as melts, as solutionsof such mixtures in water or other solvents, or as solids in which theurea-sulfuric acid component is impregnated or exchanged into a solidsupport such as carbon, refractory oxides such as silica, alumina, andthe like, acid or basic ion exchange resins or zeolites such as thenatural and synthetic aluminosilicates, and combinations of suchsupports. The catalysts may also contain optional components such assurfactants and transition metal halides. Other components that do notsubstantially negate the proton-donating activity of themonourea-sulfuric acid adduct may also be present.

The urea-sulfuric acid components may also contain unreacted (free)sulfuric acid or the diurea adduct of sulfuric acid. The useful andpreferred proportions of urea, sulfuric acid, and of the mono- anddiurea adducts of sulfuric acid, relative to each other, can beconveniently expressed in terms of the urea/sulfuric acid molar ratio.This ratio will usually be within the range of about 1/4 to about 7/4,preferably about 1/2 to about 3/2, and most preferably between about 1/1to about 3/2. Urea/sulfuric acid molar ratios within the range of about1/4 to about 7/4 define compositions in which at least 25 percent of thesulfuric acid is present as the monourea sulfuric acid adduct. Molarratios within the range of 1/2 to about 3/2 define compositions in whichat least 50 percent of the sulfuric acid is present as the monoureaadduct. The most preferred molar ratio range of about 1/1 to about 3/2defines compositions which contain essentially no uncomplexed sulfuricacid and in which at least 50 percent of the sulfuric acid is present asthe monourea-sulfuric acid adduct. The most preferred combinations haveurea/sulfuric acid molar ratios of about 1/1. In such compositionsessentially all of the sulfuric acid is present as the monourea-sulfuricacid adduct, and such compositions are essentially free of uncomplexedsulfuric acid. Substantial amounts of uncomplexed sulfuric acid, i.e.,sulfuric acid that is not complexed with urea as either the mono- ordiurea adduct, are unpreferred since sulfuric acid, when present insubstantial amounts, may promote side reactions such as oxidation,sulfonation and/or other reactions. While excess urea is generally notdetrimental to the performance of the urea-sulfuric acid components asacid catalysts for organic reactions, the presence of excess urea abovethe amount required for a urea/sulfuric acid molar ratio of 1/1, resultsin the conversion of a portion of the monourea-sulfuric acid adduct tothe diurea adduct which has little or no proton-donating ability. Thus,the diurea adduct has little or no activity as a catalyst foracid-catalyzed organic reactions.

The solutions of the urea-sulfuric acid component useful in the methodsof this invention contain a catalytically active amount of themonourea-sulfuric acid adduct. Very low monourea adduct concentrations,e.g., on the order of about 0.5 weight percent of the solution or melt,are sufficient to promote a variety of acid-catalyzed organic reactions.However, higher concentrations of the monourea-sulfuric acid adduct aregenerally preferred. Thus, solutions of the urea-sulfuric acid componentemployed as catalysts in the methods of this invention will usuallycontain at least about 0.5, generally at least about 1, preferably atleast about 5, and most preferably at least about 10 weight percent ureaand sulfuric acid based on the combined weight of those two components.Even higher concentrations of urea and sulfuric acid provide increasedcatalytic activity. Thus, solutions containing at least 50 percent, andeven 85 weight percent or more of the combination of urea and sulfuricacid can be used. Accordingly, the urea and sulfuric acid, incombination, will usually constitute 0.5 to about 90, normally about 1to about 90, and preferably about 5 to about 90 weight percent of thesolutions employed in the methods of this invention.

The solutions of the urea-sulfuric acid component may contain anysolvent suitable for dissolving the urea-sulfuric acid component underthe reaction conditions employed. Suitable solvents include polarsolvents such as water, dimethylsulfoxide (DMSO), halogenatedhydrocarbons such as trichloromethane, oxygenated hydrocarbons such asmethylethylketone and tetrahydrofuran, and the like. The solvent ispreferably not reactive with the urea-sulfuric acid component, theorganic feed, intermediates or products, or other components employed inthe acid-catalyzed organic reactions encompassed by the methods of thisinvention, unless, of course, the organic feed is also employed as thesolvent for the urea-sulfuric acid component.

Melts of the urea-sulfuric acid component-containing compositions thathave melting points above ambient temperature, e.g., above 70° F., canalso be employed to catalyze the acid-catalyzed organic reactionsencompassed by the methods of this invention. The urea-sulfuric acidcomponents useful in this embodiment are solids at ambient temperatureand are converted to melts by heating them to elevated reactiontemperatures. Within this embodiment, the melts will usually contain atleast about 50, and preferably at least about 80 weight percent of theurea-sulfuric acid component based on the combined weight of urea andsulfuric acid. The melts will usually contain at least about 20,generally at least about 50, preferably at least about 80, weightpercent of the preferred monourea-sulfuric acid adduct.

The compositions employed in the methods of this invention may alsocontain one or more surfactants. The surfactant employed in thecomposition is preferably, although not necessarily, chemically stablefor a significant period of time in the presence of the urea-sulfuricacid component and in the presence of other components employed in themethods of this invention. The surfactants increase the activity of theurea-sulfuric acid component toward essentially all non-polar organiccompounds including lipophilic organic materials such as waxes,proteins, ligands, fats, alkanes, high molecular weight acids, alcohols,and the like. For instance, surfactants enhance the activity of theliquid urea-sulfuric acid compositions employed in the methods of thisinvention toward cellulosic material such as growing or harvestedvegetation which is coated with or which contains a significant amountof waxy cuticle. Thus, surfactants enhance the acid-catalyzed hydrolysisof lipid-containing cellulosic materials and increase the herbicidalactivity of the urea-sulfuric acid component toward growing vegetationas discussed hereinafter and in my copending application Ser. No.444,667 referred to above and incorporated herein by reference. Theherbicidal activity of the described urea-sulfuric acid components isapparently due, at least in part, to their ability to catalyze thechemical conversion of cellulose and/or other organic compounds in plantmatter. As described herein, these urea-sulfuric acid components arecapable of catalyzing reactions involving organic compounds other thanplant matter, as well.

The selected surfactant is preferably sufficiently chemically stable inthe liquid or solid compositions, or in the melts formed from the solidcompositions, to assure that the surfactant retains sufficient wettingability toward the organic material to be converted, for a period oftime required to manufacture, store, transport and employ theurea-sulfuric acid component. The stability of any surfactant can bereadily determined by adding an amount of the surfactant to theurea-sulfuric acid composition in which it is to be employed andmonitoring the combination by conventional nuclear magnetic resonance(NMR) analytical techniques. NMR can be used to monitor the frequencyand magnitude of spectral peaks characteristic of a selected nucleus,e.g., a hydrogen nucleus in the surfactant. Persistent spectral peakmagnitude and frequency over a period of 5 to 6 hours indicatestability. Diminished peak magnitude, or a shift in peak frequencyassociated with the selected nucleus, indicates instability, i.e., thatthe arrangement of functional groups in the surfactant molecule has beenmodified.

Illustrative of classes of stable surfactants are nonionics such as thealkylphenol polyethylene oxides, anionics such as the long chain alkylsulfates, and cationics such as 1-hydroxyethyl-2-heptadecenylgloxalidin. Of these, the polyethylene oxide nonionic surfactants areparticularly preferred. Illustrative of preferred specific surfactantsis the nonionic surfactant marketed by Thompson-Hayward, Inc., under thetrademark T-MULZ 891.

The surfactant concentration is preferably sufficient to increase thewetting ability of the urea-sulfuric acid component for the organicmaterial to be converted. Even very minor surfactant concentrations willincrease the wetting ability of the urea-sulfuric acid component to someextent. Surfactant concentration will usually be at least about 0.05,generally at least about 0.1, and preferably at least about 0.2 weightpercent of the solution as it is employed in the methods of thisinvention. Surfactant concentrations of about 0.2 to about 1 weightpercent are adequate in most applications.

The urea-sulfuric acid component employed in this invention can becombined with transition metal halides to form the conjugate acid of themonourea-sulfuric acid adduct with the transition metal halide. Suchconjugate acids of transition metal halides, such as Friedel-Craftscatalysts and the transition metal halides employed in the so-calledZeigler catalysts, are discussed in the Kirk-Othmer publication referredto above and in U.S. Pat. Nos. 4,078,832, 3,987,123, 4,086,062 and4,008,360, all of which are incorporated herein by reference. Forinstance, at page 856 of Volume 12, Kirk-Othmer describes the complex ofhydrochloric acid with aluminum trichloride. The transition metal halidecomponent of the conjugate acid Friedel-Crafts catalysts of thisinvention can comprise halides of any transition metal, particularly thehalides of aluminum, vanadium, boron, titanium, tin, gallium, andcombinations thereof. The halide component can be selected fromchloride, bromide, fluoride and iodide, although the iodides are lessactive for the promotion of acid-catalyzed organic reactions andaccordingly are less preferred. The conjugate Friedel-Crafts catalystsof this invention can comprise equi-molar amounts of themonourea-sulfuric acid adduct and the transition metal halide, or theycan comprise an excess of either one of these two components. It ispresently preferred, however, that the conjugate acid contain about 0.1to about 2 moles of transition metal halide for each mole of themonourea-sulfuric acid adduct in the composition.

The urea-sulfuric acid components useful in the compositions and methodsof this invention can be produced by the reaction of solid urea andsulfuric acid by the methods described in my copending application Ser.No. 318,629 filed Nov. 5, 1981 now U.S. Pat. No. 4,445,925 thedisclosure of which is incorporated herein by reference. Theurea-sulfuric acid components produced in accordance with the methodsdescribed in the above-referenced copending application are free ofdecomposition products of urea, sulfuric acid and of the mono- or diureasulfuric acid adduct, and are particularly preferred for that reason. Asdescribed in my U.S. Pat. No. 4,445,925 the reaction of urea andsulfuric acid to produce the urea-sulfuric acid components used in thecompositions and methods of this invention is extremely exothermic and,if not adequately controlled, can result in the decomposition ofreactants or products and in the formation of decomposition productssuch as sulfamic acid, ammonium sulfamate, ammonium sulfate, and othermaterials. The formation of such decomposition products, and thepresence of such decomposition products in the compositions and methodsof this invention, is unpreferred for several reasons. The presence ofdecomposition products may interfere with the acid-catalyzed conversionof organic compounds, or it may result in the introduction of impuritiesinto the desired product. Decomposition also results in the loss ofactive sulfuric acid which must be available to combine with urea toproduce the active monourea-sulfuric acid adduct contained in thecompositions useful herein.

Solid urea-sulfuric acid components useful in producing the melts andsolutions employed in the methods of this invention can be obtained bycrystallization from their respective aqueous solutions, as described inmy copending application Ser. No. 444,667, "Methods for ControllingVegetation", filed Nov. 26, 1982. The surfactant, when present, willeither crystallize at approximately the same temperature as theurea-sulfuric acid component or will be entrained with the crystallizedurea-sulfuric acid component. In the alternative, the surfactant can beadded, when desired, to the dry or damp urea-sulfuric acid component byany suitable mixing technique after crystallization of the urea-sulfuricacid component from its solution.

As described in my copending application Ser. No. 444,667, theurea-sulfuric acid aqueous solution there referred to as 18-0-0-17 has acrystallization temperature of 50° F. Designations such as 18-0-0-17 areconventionally used in the agricultural industry to define the weightpercentages of nitrogen, phosphorus, potassium and a fourth component,in this case sulfur, contained in a composition. Thus 18-0-0-17 contains18 weight percent nitrogen as urea, 0 percent phosphorus, 0 percentpotassium, and 17 weight percent sulfur. The 18-0-0-17 solution has aurea/sulfuric acid molar ratio of about 1.2 and contains about 90 weightpercent of a combination of urea and sulfuric acid. Urea and sulfuricacid, in combination, constitute 80 weight percent of the aqueoussolution designated as 10-0-0-19 in copending application Ser. No.444,667, which composition has a urea/sulfuric acid molar ratio of about0.6 and which crystallizes at about 42° F. The aqueous solutiondesignated as 9-0-0-25 comprises approximately 96 weight percent of acombination of urea and sulfuric acid, has a urea/sulfuric acid molarratio of about 0.4, and crystallizes at 14° F. The indicatedcrystallization temperatures of the three urea-sulfuric acid aqueoussolutions referred to immediately above, and the crystallizationtemperatures for other formulations of urea and sulfuric acid useful inthe composition and methods of this invention, are illustrated, in part,by the isotherms in the ternary phase diagram for urea, sulfuric acidand water in the drawing accompanying copending application Ser. No.444,667. The crystallization temperatures for other urea-sulfuric acidcombinations useful in the compositions and methods of this inventioncan be determined from that drawing or by cooling the selected solutionuntil crystallization occurs. The crystallized material can be separatedfrom the supernant aqueous phase by any suitable solid-liquid separationtechnique such as filtration, centrifugation, decanting, and the like,and the recovered damp solid can be dried by evaporation if desired.

Since lower crystallization temperatures are required to separate thedesired urea-sulfuric acid component from the more dilute solutions, itis preferable to begin with more concentrated solutions having highercrystallization points such as the 18-0-0-17 composition which containsonly about 10 percent water. More concentrated solutions, and thosehaving higher crystallization temperatures, e.g., 77° F., are even morepreferred since less cooling is required to obtain a similar quantity ofthe urea-sulfuric acid component.

Substantially anhydrous solid compositions can be obtained by washingthe dried, crystallized urea-sulfuric acid component with a stronglyhydrophillic solvent such as absolute ethanol or acetone. Ten to 100weight parts solvent per weight part solute are usually adequate forthis purpose.

The anhydrous monourea adduct-containing component is stable at ambientconditions and has negligible vapor pressure up to its decompositiontemperatures of about 300° F. Decomposition temperatures of theanhydrous solids do not change significantly with changes incomposition. These compositions decompose almost explosively at muchlower temperatures, e.g., 176° F. and below, in the presence of water.

The most preferred solid composition consisting of the 1/1 urea/sulfuricacid molar adduct has a melting point of about 100° F., and the meltingpoint of the urea-sulfuric acid component increases as the urea/acidratio deviates from 1:1 in either direction in a manner paralleling theisotherms illustrated in the drawing of Ser. No. 444,667.

The liquid urea-sulfuric compositions employed in the methods of thisinvention can be produced by any method capable of producing a solutionof the desired composition. Thus, the surfactant and/or othercomponents, when used, can be added to the concentrated urea-sulfuricacid solution during or immediately after its manufacture by the processdescribed in my U.S. Pat. No. 4,445,925 referred to above, or suchcomponents can be added to the urea-sulfuric acid solution prior to itsuse to catalyze organic reactions in accordance with the methods of thisinvention. Alternatively, the optional components, when employed, can bemixed with the amount of the selected solvent required to produce aconcentrated or dilute solution, as desired, before or concurrently withthe solid or concentrated urea-sulfuric acid component. Of course,dissolution of the solid urea-sulfuric acid compositions described abovethat contain the desired optional components in the selected solventwill also result in the formation of the active liquid compositions ofthis invention. The melts employed in several embodiments of thisinvention can be produced simply by melting the selected solidcomposition, either prior to or during contact with the organic materialto be converted as described hereinafter.

The conjugate Friedel-Crafts acids of this invention can be prepared byreacting the urea-sulfuric acid component with one or more transitionmetal halides. The reaction can be conducted by dissolving theurea-sulfuric acid component in a polar solvent such as those describedabove, and dissolving or dispersing the transition metal halide in theresulting solution. Agitation and elevated temperatures such astemperatures within the range of about 90° to about 150° F. increase therate of formation of the conjugate acid, i.e., the combination of themonourea-sulfuric acid adduct and transition metal halide.

The reactant-containing compositions of this invention can be preparedby mixing one or more organic and/or inorganic reactants, such as thosediscussed hereinafter, with one or more of the urea-sulfuric acidcomponents useful in the methods of this invention including theconjugate Friedel-Crafts catalysts of this invention, in the presence orabsence of an added solvent or surfactant. These compositions can beeither homogeneous solutions or heterogeneous mixtures includingliquid-liquid, solid-liquid and vapor-liquid mixtures of theurea-sulfuric acid and/or conjugate acid components and one or moreliquid, solid or vaporous reactants.

The novel methods of this invention involve acid-catalyzed reactions oforganic compounds in the presence of a catalytically active amount ofthe described urea-sulfuric acid components in the presence or absenceof additional components such as surfactants, transition metal halides,and/or the conjugate Friedel-Crafts catalysts of this invention, andreference to the urea-sulfuric acid components in the description of themethods of this invention is intended to include compositions whichcontain such additional components. The novel surfactant-containingcompositions of this invention are preferred in reactions involvingrelatively lipophilic organic materials since surfactants accentuate theactivity of the urea-sulfuric acid component toward such materials.

Any acid-catalyzed organic reaction that is catalyzed by relativelystrong acids such as sulfuric acid can be carried out by the methods ofthis invention. A variety of such reactions are well known in theliterature and many are discussed in the Kirk-Othmer Encyclopedia ofChemical Technology publication referred to above and the referencesreferred to therein, the disclosures of which are incorporated herein byreference. Illustrative of the acid-catalyzed organic reactions that canbe catalyzed by the urea-sulfuric acid components useful in the methodsof this invention are (1) oxidation, such as oxidative additionreactions; (2) reduction, such as reductive addition reactions; (3)esterification; (4) transesterification; (5) hydrogenation; (6)isomerization, including racemization of optical isomers; (7) hydrolysiswhich, for the purposes of this disclosure, includes alcoholisis andthiolisis, i.e, the reaction of organic compounds with alcohols andthiols; (8) alkylation; (b 9) polymerization of olefinically unsaturatedorganic compounds; (10) Friedel-Crafts reactions; (11) demetalization;and (12) nitration reactions. Other reactions that are known to becatalyzed by acid catalysts can also be catalyzed by the urea-sulfuricacid components described herein. The specific methods discussedhereinafter can be catalyzed by any one of the urea-sulfuric acidcatalyst components discussed above including the surfactant and/ortransition metal halide-containing components.

Acid-catalyzed oxidative reactions primarily involve the abstraction ofhydrogen from an organic compound by reacting the compound with anoxidant. An illustrative example of such reactions is the oxidativeaddition of organic compounds illustrated by the following expression:

    R.sub.1 H+R.sub.2 H+1/2O.sub.2 →R.sub.1 R.sub.2 +H.sub.2 O (1)

wherein R₁ and R₂ are the same or different hydrocarbyl radicalsincluding straight and branched chain alkanes; alkenes; alkynes;aromatics; alkyl-, alkeny-, and alkynyl-substituted aryls; andaryl-substituted alkanes, alkenes and alkynes, of essentially anymolecular weight, but usually having from 1 to about 40 carbon atoms permolecule. Preferred reactants include olefins, particularlyalpha-olefins.

The acid-catalyzed oxidation reactions can be promoted in accordancewith this invention by contacting the organic compound to be convertedwith the catalyst component in the presence of an oxidant, which ispreferably oxygen as illustrated in the above equation. The oxidativeaddition reaction illustrated in the equation requires only that theorganic compound contain a carbon-to-hydrogen bond capable of undergoingoxidative addition reactions. The organic compound can be eitherdispersed or dissolved in a melt or solution of the catalyst componentin an appropriate solvent, or it can be contacted with the catalystcomponent by conventional mixing and contacting procedures.

Acid-catalyzed reduction reactions of organic compounds in accordancewith the methods of this invention may involve the addition of hydrogento unsaturated organic compounds. Illustrative reactions include thehydrogenation of organic compounds containing olefinic, alkynyl oraromatic unsaturation, and reductive addition reactions such asdimerization, oligermerization and polymerization reactions asillustrated schematically in the following expression: ##STR1## whereinR₁, R₂, R₃ and R₄ are the same or different functional groups selectedfrom hydrogen and alkyl moieties having from 1 to about 20 carbon atoms.Preferred reactants include normal and branched chain alkenes andalkenyl aromatic compounds. The acid-catalyzed reduction reactions canbe conducted by contacting the organic compound to be converted with areducing agent such as hydrogen, hydrazine, and/or other reducingagents, in the absence of oxidants. Such reactions can be carried out byforming a composition such as a melt, solution or dispersion containingthe unsaturated organic compounds, the reducing agent, and theurea-sulfuric acid component in the absence of oxidants under conditionsof temperature and pressure sufficient to promote the reductive additionreaction. As illustrated by the Examples discussed hereinafter, thereductive addition of propylene can be promoted at ambient temperature.

Acid-catalyzed esterification reactions in accordance with the methodsof this invention typically involve reacting an esterifiable organiccompound having one or more amide, nitrile, carboxylic acid, carboxylicacid anhydride, acyl halide, and/or thiocarboxylic acid groups, with anorganic alcohol or thiol in the presence of acid catalyst component.Such reactions can be conducted by contacting a composition containingthe urea-sulfuric acid catalyst component useful in the methods of thisinvention, one or more esterifiable organic compounds, and one or morealcohols, thiols and/or amines, under esterification conditions.Reactions of acids, amides and thioacids are illustrated by thefollowing expression: ##STR2## wherein R₁ and R₂ are any organicradicals including natural and synthetic polymers such as partiallyhydrolyzed protein or cellulose, nylon, dacron, etc., and Y and Z arethe same or different divalent radicals selected from oxygen, sulfur andNH groups. X is any integer of 1 or greater and can range up to 1000 ormore, depending upon the molecular weight of the compound involved. Forinstance, partially hydrolyzed polymers such as those referred to abovecan contain 100 or more functional groups capable of undergoingesterification by the acid-catalyzed methods of this invention.

The reaction of alcohols, thiols, and amines with organic cyanides andacyl halides, while not illustrated in expression (3) above, arewell-known reactants, which, in the present invention, are catalyticallypromoted by the urea-sulfuric component. For instance, the reaction ofalcohols with acyl chlorides may be catalyzed by the method of theinvention to form the corresponding ester and hydrogen chloride and thereaction of organic cyanides with water and/or alcohols results in theformation of the corresponding ester and ammonia, as discussed inKirk-Othmer, Vol. 9, page 302. The evolution of ammonia byesterification of nitriles and amides may result in the consumption ofsome of the sulfuric acid in the urea-sulfuric acid component employedin the methods of this invention but will not prevent the occurrence ofacid-catalyzed esterification. Sulfuric acid consumed by ammonia or byother bases produced or present in esterification reactions or in otheracid-catalyzed reactions encompassed by the methods of this inventioncan be replaced by adding makeup sulfuric acid during the process ifdesired.

Although expression (3) above indicates that all of the acyl moietiesare associated with one organic radical indicated by R₁, and that all ofthe alcohol, thiol and/or amine moieties are associated with one organicradical identified as R₂, that form of expression is employed only inway of illustration. For instance, a multifunctional carboxylic acid canbe esterified by a number of monofunctional alcohols; conversely, anumber of monofunctional carboxylic acids, thio-acids, etc., can beesterified by fewer molecules of a polyfunctional alcohol, thiol, etc.

Essentially any transesterification reaction can be conducted by themethods of this invention including (a) ester-ester interchange, (b)alcoholisis which involves exchange of alcohol, thiol or amino groups,and (c) acidolysis which involves interchange of carboxylic acid,thiocarboxylic acid and/or amide groups. Such transesterificationreactions can be conducted by contacting a composition containing (1)the urea-sulfuric component useful in this invention, (2) a carboxylicacid ester, thioester, and/or amido-ester, and either (3) a dissimilarorganoester, thioester and/or amido-ester, or (4) a carboxylic acid,thioacid, or amide, or (5) an alcohol, thiol, and/or amine, orcombinations of (3), (4) and (5), under esterification conditions. Suchreactions are illustrated schematically by the following expressions:##STR3## As in the case of esterification illustrated by expression (3)above, the R₁, R₂, R₃ and R₄ moieties involved in expressions 4(a), (b),and (c) can be the same or different organic moieties of essentially anymolecular weight, Y and Z are the same or different divalent radicalsselected from oxygen, sulfur and NH groups, and x represents any integerof 1 or greater. Also as in the case of esterification, compoundscontaining one or more ester groups can be reacted either with mono- orpolyfunctional esters, alcohols, thiols, acids, thioacids, etc. Forinstance, alcohols such as 1-butanol can be reacted with either simpleesters such as ethyl acetate to produce butylacetate, or with complexpolyamides such as proteins to produce the corresponding butyl esters ofaminoacids contained in the protein.

The acid-catalyzed hydrogenation reactions of this invention can beconducted by contacting a composition containing (1) an organic compoundcontaining carbon-to-carbon unsaturation, (2) hydrogen, and (3) theurea-sulfuric acid-containing catalysts useful in the methods of thisinvention, under hydrogenation conditions. The reaction can be conductedby exposing a composition containing the acid catalyst component,hydrogen, and an unsaturated organic compound under conditions oftemperature and pressure sufficient to promote hydrogenation. Thehydrogenation of olefins is illustrated by expression (5).

    R.sub.1 --CH═CH ).sub.x R.sub.2 +xH.sub.2 →R.sub.1 --CH.sub.2 -CH.sub.2).sub.x R.sub.2                                  ( 5)

wherein R₁ and R₂ are the same or different hydrogen or organic moietiesof essentially any molecular weight and x is any integer of 1 orgreater. For example, the methods of this invention can be employed tohydrogenate ethylene as well as polymers having molecular weights of100,000 or greater, which polymers contain a plurality of olefin bonds.They can also be employed to hydrogenate benzene, alkyl or alkenylaromatics, alkynes, and other unsaturated organic compounds.Olefinically unsaturated organic compounds, particularly hydrocarboncompounds, having 2 to about 40 carbon atoms are presently preferred.The hydrogenation reactions in accordance with the methods of thisinvention can be promoted by hydrogen, hydrazine, or other hydrogenatingagents, and are preferably conducted in the absence of oxidizing agentssuch as oxygen and other oxidants.

The acid-catalyzed isomerization reactions conducted in accordance withthe methods of this invention involve the isomerization of any organiccompounds having 4 or more carbon atoms by contacting such compoundswith the acid-catalyst component useful in the methods of this inventionunder isomerization conditions. Such isomerization reactions can beconducted by contacting a composition containing the acid catalystcomponent and one or more isomerizable organic compounds underisomerization conditions. Essentially any organic compounds can beisomerized by the methods of this invention including hydrocarbons andorganic compounds containing elements other than carbon and hydrogensuch as oxygen, sulfur, phosphorus, nitrogen, and the like. Theexistence of functional groups in organic compounds employed in theacid-catalyzed isomerization reactions of this invention which arereactive in the presence of the acid catalyst component may result inthe occurrence of other reactions in addition to isomerization.Nevertheless, isomerization will also occur.

The isomerization reactions encompassed by the methods of this inventionare particularly useful for the isomerization of relatively lowmolecular weight hydrocarbons having 4 to about 20 carbon atoms permolecule. They are also useful for the racemization of optical isomers,i.e., the conversion of dextro or levorotatory isomers to thecorresponding racemic mixture.

The acid-catalyzed hydrolysis reactions encompassed by the methods ofthis invention include the reaction of water, alcohols, thiols, oramines with (a) carboxylic acid amido esters including polyamides; (b)carboxylic acid esters and polyesters such as proteins, i.e., polyaminoacid esters; (c) thiocarboxylic acid esters and polyesters; (d) ethersand thioethers including polyoxyethers and thioethers such as cellulose,rayon, starches, and other polysaccharides; (e) di- and poly-alkylaminesincluding polyamines; (f) organic compounds containing olefinicunsaturation; and (g) expoxides. Such hydrolysis reactions can beconducted by contacting a composition containing (1) the urea-sulfuricacid component employed in the methods of this invention, (2) an organiccompound having one or more hydrolyzable functional groups such as amidoester, acid ester, thioester, ether, thioether, amino, olefinic, and/orepoxy linkages, and (3) a hydrolyzing compound such as water, alcohols,thiols, and/or amines under conditions of temperature and pressuresufficient to promote hydrolysis of the hydrolyzable functional group.In the alternative, the organic compound containing a hydrolyzablefunctional group such as amido ester, acid ester, etc., can be contactedwith a composition containing the urea-sulfuric acid-containing acidcatalyst employed in the methods of this invention and a hydrolyzingcompound under hydrolyzing conditions.

Several of the hydrolysis reactions encompassed by this embodiment ofthe invention are also encompassed by the transesterification methods ofthis invention which involve alcoholosis as discussed above. Suchreactions include the reaction of alcohols, thiols and/or amines with(1) mono- or polycarboxylic acid esters or polyesters; (2) mono- orpolyfunctional thiocarboxylic acid esters or polyesters; and (3) mono-or polycarboxylic acid amido-esters or polyamido esters.

A particularly interesting aspect of the hydrolysis reactions which canbe effected in accordance with the methods of this invention is thatthey can be employed for either the partial or the complete hydrolysisof natural and synthetic polymers such as polysaccharides includingcellulose, starches, and the like, protein, rayon, nylon, and others, bycontacting such materials with the acid catalyst components of thisinvention containing water. Such reactions proceed even at ambienttemperature and, if allowed to go to completion, they result in completedepolymerization, i.e., complete hydrolysis of the polymer. For example,cellulose can be converted completely to glucose and proteins can beconverted to amino acids by this method. Furthermore, the partialhydrolysis of cellulose appears to account for the dramatic herbicidalactivity of the urea-sulfuric acid component employed in the methods ofthis invention. The herbicidal activity of the urea-sulfuric acidcomponent is discussed in more detail in my copending application Ser.No. 444,667. The ability of surfactants to accentuate the activity ofthe urea-sulfuric acid component and to broaden the variety ofvegetation that can be controlled by the use of the urea-sulfuric acidcomponents useful in the methods of this invention is also discussed insaid copending application.

The hydrolysis reactions encompassed by the methods of this inventionare illustrated, in part, by the following expressions which areintended only to be schematic representations of several of theacid-catalyzed hydrolysis reactions encompassed by the methods of thisinvention: ##STR4## Expression 6(a) represents the completeacid-catalyzed hydrolysis of amino acid esters, including poly-aminoacid esters such as proteins, by reaction with a hydrolyzing agent. Inaccordance with expression 6(a), R₁ can be any difunctional organicmoeity, Y can be hydrogen or a monofunctional terminal organic moiety, Zis a monofunctional organic or inorganic moiety such as potassium orother metal ion, R₂ is hydrogen or any organic moiety includinghydrocarbyl radicals having 1 to 20 carbon atoms per molecule, X isoxygen, sulfur, nitrogen, or a combination of these, and n is anyinteger of 1 or greater. From expression 6(a) it can be seen that thereaction of protein--a poly-alphaamino acid ester--with water, ifallowed to go to completion, results in formation of the amino acidmonomer units contained in the protein. Expression 6(b) illustrates thehydrolysis of a diorganoamine by reaction with an organo-thiol in whichR₁, R₂, and R₃ can be any organic moiety.

Expression 6(c) illustrates the hydrolysis of an organic thioester byreaction with water to produce the corresponding carboxylic acid andthiol in which R₁ and R₂ can be any organic moeity. As in the case ofthe other hydrolysis reactions encompassed by this embodiment of theinvention, alcohols, thiols and/or amines can be substituted for, orcombined with, the water illustrated in expression 6(c).

Expression 6(d) schematically illustrates the hydrolysis of an organicepoxide by the acid-catalyzed reaction of the epoxide with water,thiols, alcohols or amines, in which R₄ and R₅ are monovalent moietiesselected from hydrogen and any organic moiety, R₆ is a monovalentorganic moiety having at least 1 carbon, and X is selected from oxygen,sulfur and nitrogen.

The hydrolysis of olefins, including poly-functional olefins, withwater, alcohols, thiols, or amines, can be illustrated schematically bythe following expression ##STR5## in which R₁ and R₂ and R₃ are the sameor different monovalent moieties selected from hydrogen and any organicmoiety, X is O, S, and/or NH, and n is any integer of 1 or greater.

Alkylation reactions in accordance with the methods of this inventioninclude the reaction of any organic compound capable of being alkylatedby acid-catalyzed reaction with an organic reactant containing olefinicunsaturation. These reactions can be effected by contacting thealkylatable organic compound with a composition comprising theurea-sulfuric acid-containing acid catalysts useful in the methods ofthis invention and an organic reactant containing olefinic unsaturation,and are illustrated schematically by the following expression: ##STR6##wherein R₂ and R₃ are the same or different hydrogen or organicmoieties, particularly alkyl groups having from 1 to 10 carbon atoms,and R₁ is an alkylatable organic compound, particularly straight orbranched chain alkane, aromatic, alkyl-aromatics, and/or aryl-alkaneshaving from 4 to 20 carbon atoms per molecule.

Acid-catalyzed olefin polymerization reactions in accordance with themethods of this invention include the polymerization of at least oneorganic compound containing at least one carbon-to-carbon olefin bondcapable of undergoing acid-catalyzed polymerization by contacting theorganic compound or compounds with the urea-sulfuric acidcontainingcatalysts of this invention. In this embodiment, the reaction system ispreferably substantially oxidant-free Such polymerization reactions areillustrated schematically by the following expression: ##STR7## in whichR₁ and R₂ are selected from hydrogen or monovalent organic moieties,particularly hydrocarbyl radicals having from 1 to 10 carbon atoms, andn is the number of monomer units incorporated in the polymer. Copolymersof two or more olefinically unsaturated monomers can be produced by theacid-catalyzed polymerization reactions in accordance with the methodsof this invention. Illustrative of such copolymers arestyrene-butadiene, ethylene-propylene, methacrylic acid-ethylacrylate-hyroxyethylacrylate, and ethylene-dicyclopentadiene copolymers,and the like, including the so-called hydrocarbon resins derived fromcracked petroleum distillates, turpentine fractions, coal tar fractionsand certain olefinic monomers, such as the hydrocarbon resins discussedin Kirk-Othmer, Volume 12, at pages 852-857 and in the references citedtherein.

Friedel-Crafts reactions which can be conducted in accordance with themethods of this invention involve the reaction of organic compounds,particularly hydrocarbon compounds, capable of undergoing acid-catalyzedFriedel-Crafts reactions, with hydrocarbyl halides. Such reactions canbe effected by contacting one or more organic compounds with acomposition comprising the urea-sulfuric acid-containing catalystscompositions useful in the methods of this invention and a hydrocarbylhalide. Such Friedel-Crafts reactions are illustrated schematically bythe following expression:

    R.sub.1 H+R.sub.2 X→R.sub.1 R.sub.2 +HX             (9)

in which R₁ is a monovalent organic moiety capable of undergoingFriedel-Crafts reactions with hydrocarbyl halides, R₂ is a monovalenthydrocarbyl moiety, preferably an alkyl group having from 1 to 20 carbonatoms, and X is a halogen, preferably chlorine, bromine or fluorine,most preferably chlorine.

The acid-catalyst component employed to catalyze the Friedel-Craftsreactions in accordance with the methods of this invention can compriseany of the urea-sulfuric acid components useful in the methods of thisinvention although the urea-sulfuric acid components which contain aFriedel-Crafts halide catalyst, such as the novel conjugateFriedel-Crafts catalysts of this invention are preferred.

The acid-catalyzed demetalization reactions in accordance with themethods of this invention include the demetalization of organo-metalcompounds capable of undergoing acid-catalyzed demetalization byreaction with water and/or alcohols, and they can be effected bycontacting a composition containing such organo-metal compounds, theurea-sulfuric acid-containing catalysts useful in the methods of thisinvention, and water and/or alcohols, under conditions of time andtemperature sufficient to obtain the desired degree of demetalization.Such demetalization reactions are illustrated by the followingexpression:

    (R-.sub.a M.sup.a +aH.sup.+ →aRH+M.sup.+a           ( 10)

wherein R is any organic radical including phorphins and petrophorphins,M is any metal, and a is the valence of the metal associated with theorganic moiety. Organic complexes of zero-valent metals can also bedemetalized by these methods. Illustrative of the organo-metal compoundsthat can be demetalized by reaction with water and/or alcohol inaccordance with the methods of this invention are the phorphins andpetrophorphins commonly found in petroleum crudes, tar-sand oils, shaleoils, coal extracts, and the like.

The acid-catalyzed demetalization reactions in accordance with themethods of this invention can be conducted in the presence of an oxidantsuch as oxygen, peroxides, ozone, and the like, to oxidize the metalcontained in the organo-metal compound to a more soluble, higher valencestate when desired. Such oxidative demetalization conversions can beeffected by contacting a composition containing the organo-metalcompound, the urea-sulfuric acid components useful in the methods ofthis invention, and the oxidant. Similarly, the valence state of themetal complexed n the organo-metal compound can be reduced to produce amore soluble metal ion, e.g., the conversion of ferric to ferrous iron,by conducting the acid-catalyzed demetalization reaction in accordancewith this invention in the presence of a reducing agent such ashydrogen, hydrazine, and the like. Such reductive acid-catalyzeddemetalization reactions can be conducted by contacting a compositioncontaining the organo-metal compound, the urea-sulfuric acid component,and a reducing agent.

The acid-catalyzed nitration reactions of this invention involve thereaction of organic compounds capable of undergoing acid-catalyzednitration with nitrogen oxides, particularly with nitric oxide, and canbe effected by contacting a composition containing the nitratablecompound, nitrogen oxides, and the urea-sulfuric acid-containingcatalyst under nitration conditions. Such reactions are illustratedschematically by expression (11).

    R(H).sub.n +nNO.sub.2 →(NO.sub.2).sub.n R+.sub.n H.sup.+( 11)

in which R is any nitratable organic moiety having a valence of n.Illustrative of nitration reactions that be conducted in accordance withthis invention are the reaction of toluene with nitric oxide to producenitrotoluene and trinitrotoluene (TNT), the nitration of cellulose toproduce nitrocellulose, the nitration of alkanes such as n-decane toproduce monoor polynitrated alkanes such as nitrodecane, and the like.

The acid-catalyzed organic reactions discussed above, and other acidcatalyzed reactions known in the art, in accordance with the methods ofthis invention, can be effected by contacting the organic material to bereacted in either vapor phase, liquid phase, or solid phase (as in thecase of cellulose, nylon and other solid materials), with the liquid orsolid urea-sulfuric acid-containing catalyst. The liquid catalysts cancomprise a melt of the anhydrous urea-sulfuric acid catalyst component,or it can comprise a solution of that component in either the organicfeed material or other solvent, and the solid catalysts can comprise theurea-sulfuric acid component, with or without the described optionalcomponents, impregnated or ion-exchanged into a solid support. Mixedliquid phase reactions can be conducted by forming emulsions ordispersions of the urea-sulfuric acid component melt or solution and thereactants and/or organic material to be converted. The novel surfactantcontaining urea-sulfuric acid components of this invention areparticularly suitable for use as acid catalysts in the conversion oforganic materials containing significant amounts of lipophilicsubstances such as waxes, oils, and high molecular weight organicsubstances. Illustrative of such lipophilic materials are the waxycuticle on many types of vegetation, proteins, particularlyfat-containing proteins, cellulosic substrates containing ligands andother lipophilic substances derived from wood, and the like.

The acid-catalyzed reactions in accordance with the methods of thisinvention can be conducted at any temperature below the thermaldecomposition temperature of the urea-sulfuric acid component and abovethat temperature at which the composition comprising the urea-sulfuricacid component solidifies. The reaction temperature should also bemaintained below the temperature at which the organic feed material,reactants, intermediates, or products react with the urea-sulfuric acidcomponent. The occurrence of any such side reactions at any givenreaction temperature can be readily determined by analyzing the productto determine the presence of by-products resulting from such sidereactions. In general, reaction temperatures should be maintained below176° F. and preferably below about 170° F. in reactions in which asignificant amount of water is present due to the relatively lowdecomposition temperature of the urea-sulfuric acid component in thepresence of water. Higher reaction temperatures up to about 300° F. canbe employed under anhydrous conditions when the reaction system issubstantially free of water, i.e., when the system contains less thanabout 2 weight percent water based on the concentration of urea-sulfuricacid component. However, such higher temperatures, i.e., temperaturesabove 170° F., are preferably avoided unless the reaction system isessentially water-free, i.e., does not contain any detectable amount ofwater. Reaction rate increases as temperature is increased.

The methods of this invention can be conducted at essentially anypressure and even under vacuum if desired. Vapor phase reactions, i.e.,reactions involving organic reactants in the vapor phase, can beaccelerated by increasing the pressure on the system. Illustrativereaction pressures are 0 to 2,000 atmospheres although pressures of 0 to100 atmospheres are usually sufficient to achieve acceptable reactionrates.

The acid-catalyzed reactions carried out in accordance with the methodsof this invention require contact times of the organic reactants and theurea-sulfuric acid component commensurate with the desired productyield. Generally, increasing the contact time increases the conversion.Since reaction rate depends upon the nature of the reaction involved,the compatability of the urea-sulfuric acid-containing component withthe reactants, and the operating pressure and temperature, the reactiontime should be sufficient to obtain the degree of conversion required.Batch contact times of one minute to 100 hours are usually sufficient toaccomplish complete conversion of most organic substrates. Shorterreaction times will usually be involved in continuous processesemploying the methods of this invention in which case it may bedesirable to separate unreacted organic materials from the effluent ofthe reaction zone and to recycle those materials to the reaction zone.

The novel compositions and acid-catalyzed methods of converting organiccompounds in accordance with this invention have several significantadvantages over compositions and methods otherwise available to the art.The urea-sulfuric acid components are relatively inexpensive; inaddition, they are non-corrosive and stable under normal conditions.They are also highly active protonating agents and therefore can beemployed in the methods of this invention to effect the acid-catalyzedconversion of a wide variety of organic compounds without promoting sidereactions associated with other acid catalysts, particularly sidereactions associated with the use of sulfuric acid such as oxidation andsulfonation.

The invention is further described by the following examples which areillustrative of specific modes of practicing the invention and are notintended as limiting the scope of the invention as defined by theappended claims.

EXAMPLE 1

This example illustrates the hydrolysis of complex polyethers bydemonstrating the complete hydrolysis of cellulose to glucose in thepresence of the urea-sulfuric acid components of this invention. Sterilecotton swabs are dissolved in a urea-sulfuric acid component having aurea/sulfuric acid molar ratio of 1.2 and containing 38.6 weight percenturea, 52.1 weight percent sulfuric acid, and 8.3 weight percent waterwhich is maintained at a temperature of 70° F. The cotton swabs areadded sequentially to approximately 500 ml. of the describedurea-sulfuric acid component and the mixture is stirred throughout theoperation. Complete dissolution of each cotton swab occurs inapproximately one minute. After the addition of approximately 20 cottonswabs the mixture becomes more viscous. A quantity of the reactantmixture is analyzed by high precision liquid chromatography (HLPC) andis found to contain glucose in an amount which corresponds to thestoichiometric conversion of the cellulose feed to the reaction. Neitherthe HLPC analysis nor any other observation during the operationindicates the occurrence of any reaction other than the hydrolysis ofcellulosic to glucose. There is no evidence of sulfonation or oxidationof either the cellulose or glucose. No fumes are emitted and thereaction medium does not discolor during the process.

EXAMPLE 2

This example illustrates the use of the urea-sulfuric acid components ofthis invention to acid-catalyze the hydrolysis of cellulose in livingvegetation and the consequent efficacy of the urea-sulfuric acidcomponents as herbicides.

Four replicated test plots of five acres each comprising onions at thefirst true-leaf stage (approximately one-inch high) infested with malva,cheese weed, nightshade, shephards purse, peneapple weed and purslane,are each treated by foliar application of 50 gallons per acre of aurea-sulfuric acid component having a urea/sulfuric acid molar ratio ofapproximately 1.1 and containing 14.6 weight percent urea, 20.8 weightpercent sulfuric acid and 64.6 weight percent water. The describedtreatment results in 95 to 100 percent kill of all weed species within48 hours after application. There is no damage to the onion crop asevidenced by the lack of foliage browning, spotting, or the like. Thecellulosic structure of the onion crop is protected by the waxy cuticlecharacteristic of green onions, which, however, can also be hydrolyzedby the use of the surfactant-containing urea-sulfuric acid componentswithin the scope of this invention.

EXAMPLE 3

This example illustrates the hydrolysis of polycarboxylic acid estersand demonstrates the depolymerization of protein by contact withurea-sulfuric acid components of this invention. Two cowhide pump sealsare contacted with a urea-sulfuric acid component in accordance withthis invention containing 36.5 weight percent urea, 52.1 weight percentsulfuric acid and 11.4 weight percent water having a urea/sulfuric acidmolar ratio of about 1.1 for approximately 70 hours at room temperature.The cowhide seals completely dissolve within the 70-hour contact period.

EXAMPLE 4

The operation of Example 3 is repeated by contacting two cowhide pumpseals with a urea-sulfuric acid component in accordance with thisinvention containing 21.5 weight percent urea, 55.2 weight percentsulfuric acid and 23.3 weight percent water having a urea/sulfuric acidmolar ratio of about 0.6. This composition corresponds to theformulation 10-0-0-18. The cowhide pump seals completely dissolve within70 hours at room temperature.

EXAMPLE 5

This example illustrates the oxidative addition of organic compounds anddemonstrates the oxidative addition of propylene in the presence of theurea-sulfuric acid components of this invention. Technical gradepropylene and air are introduced into approximately 1000 ml. of aurea-sulfuric acid component in accordance with this inventioncontaining 38.6 weight percent urea, 52.1 weight percent sulfuric acidand 9.3 weight percent water having a urea/sulfuric acid molar ratio of1.2. The gas mixture is introduced through a sparger submerged in theurea-sulfuric acid component which is maintained at 70° F. and iscontained in a three-neck five-liter flask provided with agitation, andfeed inlet and exit means. The vapor effluent from the liquid phase isremoved from the five-liter flask and passed to an ice-cooled liquidtrap in which the reaction products are collected. The liquid phaserecovered from the vapor effluent is analyzed by infrared spectroscopyand is found to contain propylene dimers and higher oligimers ofpropylene containing olefinic unsaturation.

EXAMPLE 6

Propylene and butene are reductively added to each other by introducinggaseous propylene and 2-butene into the liquid phase formed by meltingan anhydrous urea-sulfuric acid component in accordance with thisinvention containing 42.6 weight percent urea and 57.4 weight percentsulfuric acid having a urea-sulfuric acid molar ratio of 1.2. The liquidphase is maintained at a temperature of 150° F. and the vapor and liquidphases are maintained at a pressure of 1000 psig. The liquid phase iscontinuously removed from the reaction zone and flashed to recovervaporizable dimers and higher polymers of propylene and 2-butene, andcopolymers of propylene and 2-butene. Higher polymers that are notremoved by flashing can be extracted from the urea-sulfuric acid meltwith normal hexane at a pressure sufficient to maintain the normalhexane in the liquid phase. The recovered urea-sulfuric acid componentis recycled to the reaction zone.

EXAMPLE 7

Maleic acid is reacted with 1,2-ethanediol (glycol) by agitating a50--50 molar mixture of maleic acid and glycol with a urea-sulfuric acidcomponent containing 36.5 weight percent urea, 52.1 weight percentsulfuric acid and 11.4 weight percent water having a urea/sulfuric acidmolar ratio of 1.1 at a temperature of 140° F. under a pressure of 100psig. for 10 minutes to produce the corresponding polyester of maleicacid and 1,2-ethanediol. The resulting polymer is extracted from thereaction phase with isopropyl alcohol.

EXAMPLE 8

Benzene is alkylated with a mixture of 1-butene and 2-butene to producenormal and isobutylbenzenes by agitating a mixture of benzene, 1-buteneand 2-butene with a molten urea-sulfuric acid component in accordancewith this invention containing 42.6 weight percent urea and 57.4 weightpercent sulfuric acid in the presence of an alkyl phenol polyethyleneoxide surfactant at a temperature of 160° F. and under a reactionpressure sufficient to maintain the reactants in the liquid phase. Theresulting alkylbenzene is recovered by centrifuging the resultantreaction phase mixture. Complete separation is achieved by washing theurea-sulfuric acid component melt with toluene.

EXAMPLE 9

Normal-butylbenzene is prepared by heating equal molar amounts of1-chlorobutane and benzene in a molten urea-sulfuric acid component inaccordance with this invention containing 42.6 weight percent urea and57.4 weight percent sulfuric acid having a urea/sulfuric acid molarratio of 1.2 at a temperature of 140° F. and a pressure of 100 psig fora period of 10 minutes. The n-butylbenzene product is recovered bycooling the reaction mixture to solidify the urea-sulfuric acidcomponent melt and extracting the resulting mixture with toluene. Then-butylbenzene product is removed from the toluene solvent by distillingthe solvent and the urea-sulfuric acid component is re-melted andrecycled to the process.

EXAMPLE 10

A mixture of isooctanes is prepared by contacting normal octane with amolten urea-sulfuric acid component containing 42.6 weight percent ureaand 57.4 weight percent sulfuric acid and having a urea/sulfuric acidmolar ratio of 1.2 at a temperature of 160° F. under a pressure of 500psig for 5 minutes. The resulting isooctane mixture is recovered bycooling the melt to a temperature of 70° F. to solidify the moltenmixture and extracting the isooctane product with normal hexane. Theresulting solution of hexane and isooctane is separated by distillationand the urea-sulfuric acid is melted and returned to the reaction zone.

EXAMPLE 11

A petroleum crude oil containing organo-metal compounds comprisingpetrophorphins is demetalized by contacting the petroleum crude oil withan aqueous urea-sulfuric acid component in accordance with thisinvention containing 36.5 weight percent urea, 52.1 weight percentsulfuric acid and 11.4 weight percent water having urea/sulfuric acidmolar ratio of 1.1 in the presence of oxygen at a temperature of 160° F.and a pressure of 500 psig with sufficient agitation to intimately mixthe petroleum crude oil and the urea-sulfuric acid component. Theresulting petroleum crude oil of reduced metals content is recovered bydecanting from the urea-sulfuric acid component, water washed to removeresidual urea, sulfuric acid and metal salts, and dried by distillation.

EXAMPLE 12

Benzene is nitrated by forming a dispersion of benzene in a solution ofa urea-sulfuric acid component of this invention at a urea/sulfuric acidmolar ratio of 1.1 and containing 15.9 weight percent urea and 22.7weight percent sulfuric acid in water with sufficient agitation toproduce an intimate dispersion of the benzene and the urea-sulfuric acidcomponent solution. Nitric oxide is dispersed into the agitated mixtureof benzene and the urea-sulfuric acid component and the resultingmixture is contacted at a temperature of 150° F. and a pressure of 200psig. The resulting nitrated benzene product is recovered by cooling thereaction mixture and extracting the nitrated benzene product withtoluene.

While particular embodiments of this invention have been described, itwill be understood, of course, that the invention is not limited theretosince many obvious modifications can be made and it is intended toinclude within this invention any such modifications as will fall withinthe spirit and scope of the appended claims.

Having described my invention, I claim:
 1. A composition comprising asolution containing a herbicidally effective amount of the monoureaadduct of sulfuric acid and a member selected from the group consistingof surfactants, polar solvents other than water, and combinationsthereof, which composition is characterized by herbicidal activity. 2.The composition defined in claim 1 which comprises a surfactant andwater.
 3. A herbicidal composition comprising a herbicidally effectiveamount of the monourea adduct of sulfuric acid and an amount of a memberselected from the group consisting of surfactants, polar solvents otherthan water, and combinations thereof sufficient to increase the wettingability of said composition for plant foliage, which composition ischaracterized by non-selective, contact, herbicidal activity.
 4. Thecomposition defined in claim 3 which comprises a surfactant and water.5. The composition defined in claim 3 which comprises a polar solventother than water.
 6. A herbicidal composition comprising a herbicidallyeffective amount of the monourea adduct of sulfuric acid and asurfactant.
 7. A herbicidal composition comprising a solution containinga herbicidally effective amount of the monourea adduct of sulfuric acid,a surfactant, and water, and which is characterized by non-selective,contact, herbicidal activity.
 8. A composition of matter comprising themonourea adduct of sulfuric acid and a member selected from the groupconsisting of surfactants, polar solvents other than water, andcombinations thereof.
 9. The composition defined in any one of claims 1,3, 6 or 8, which further comprises water.
 10. The composition defined inany one of claims 1, 3 or 8, which comprises a surfactant.
 11. Thecomposition defined in any one of claims 1, 3 or 8 comprising a polarsolvent selected from the group consisting of dimethylsulfoxide,halogenated hydrocarbons, oxygenated hydrocarbons, and combinationsthereof.
 12. The composition defined in any one of claims 1, 3, or 8free of any unadducted sulfuric acid.
 13. The composition defined in anyone of claims 1, 3, or 8, wherein the molar ratio of equivalent urea toequivalent sulfuric acid is at least
 1. 14. The composition defined inany one of claims 1, 3, 6, 7 or 8, which is free of thermaldecomposition products of urea.
 15. The composition defined in any oneof claims 6 or 8, which comprises surfactant and water.
 16. Thecomposition defined in any one of claims 1, 3, 6, 7 or 8 which is freeof sulfamic acid and ammonium sulfamate.